WO2020042526A1 - Catalyseur composite, procédé de préparation associé et utilisation associée - Google Patents

Catalyseur composite, procédé de préparation associé et utilisation associée Download PDF

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Publication number
WO2020042526A1
WO2020042526A1 PCT/CN2019/071319 CN2019071319W WO2020042526A1 WO 2020042526 A1 WO2020042526 A1 WO 2020042526A1 CN 2019071319 W CN2019071319 W CN 2019071319W WO 2020042526 A1 WO2020042526 A1 WO 2020042526A1
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Prior art keywords
nitrogen
porous carbon
composite catalyst
doped porous
metal
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Ceased
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PCT/CN2019/071319
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English (en)
Chinese (zh)
Inventor
王勇
于丽丽
马啸
毛建拥
王哲
毛善俊
唐静思
李浩然
陈志荣
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SHANDONG NHU PHARMACEUTICAL CO Ltd
Shandong Nhu Vitamin Co Ltd
Zhejiang University ZJU
Zhejiang NHU Co Ltd
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SHANDONG NHU PHARMACEUTICAL CO Ltd
Shandong Nhu Vitamin Co Ltd
Zhejiang University ZJU
Zhejiang NHU Co Ltd
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Application filed by SHANDONG NHU PHARMACEUTICAL CO Ltd, Shandong Nhu Vitamin Co Ltd, Zhejiang University ZJU, Zhejiang NHU Co Ltd filed Critical SHANDONG NHU PHARMACEUTICAL CO Ltd
Priority to DE112019000069.1T priority Critical patent/DE112019000069T5/de
Priority to US16/669,524 priority patent/US10668460B2/en
Publication of WO2020042526A1 publication Critical patent/WO2020042526A1/fr
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/464—Rhodium
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/468—Iridium
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
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    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B01J35/45—Nanoparticles
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy

Definitions

  • the invention relates to the technical field of catalysts, in particular to a composite catalyst and a preparation method and application thereof.
  • the present invention provides a composite catalyst, a preparation method thereof, and related applications.
  • Noble metals are highly dispersed in the obtained composite catalyst, so the composite catalyst has excellent catalytic effect.
  • the invention provides a composite catalyst comprising a support and a precious metal supported on the support, the support is a nitrogen-doped porous carbon composite material, and the nitrogen-doped porous carbon composite material comprises a nitrogen-doped porous carbon.
  • Materials and metal oxides the metal oxides are uniformly distributed in the nitrogen-doped porous carbon material, the nitrogen-doped porous carbon composite material has a plurality of channels, and a part of the surface of the metal oxide passes through the channels
  • the precious metal is tightly combined with the exposed metal oxide to achieve recombination, and the precious metal is at least one of Pd, Pt, Ru, Rh, Ir, and Au.
  • the dispersion degree of the noble metal in the nitrogen-doped porous carbon composite material is 75% to 95%.
  • the mass fraction of the noble metal in the composite catalyst is 0.1% to 10%; the mass fraction of the metal oxide in the composite catalyst is 2% to 30%; the nitrogen doping
  • the mass fraction of the porous carbon material in the composite catalyst is 60% to 97.9%, and the mass fraction of the nitrogen element in the nitrogen-doped porous carbon material is 0.5% to 15%.
  • the invention also provides a method for preparing a composite catalyst, which comprises the following steps:
  • Nitrogen-containing biomass and a porogen are sequentially added to the premix, and the metal source is reacted with the porogen to obtain a mixture containing a metal precipitate, wherein the porogen is hydrogen carbonate At least one of ammonium, ammonium carbonate, ammonium oxalate, ammonium oxalate, and oxalic acid, and the molar ratio of the metal source to the porogen is 1: (1-20);
  • the mixture is first calcined under an inert atmosphere at 500 degrees Celsius to 1200 degrees Celsius to obtain a nitrogen-doped porous carbon composite material having multiple channels, wherein the nitrogen-doped porous carbon composite material includes nitrogen-doped porous Carbon material and metal oxide, the metal oxide is uniformly distributed in the nitrogen-doped porous carbon material, and a part of the metal oxide is exposed through the pores;
  • a noble metal is formed in the pores of the nitrogen-doped porous carbon composite material, so that the noble metal is tightly bound to oxygen atoms in the exposed metal oxide.
  • step 4 forming a noble metal in the pores of the nitrogen-doped porous carbon composite material is as follows:
  • the impregnated nitrogen-doped porous carbon composite material is sequentially subjected to a second calcination and hydrogen reduction, and a noble metal is formed in the pores of the nitrogen-doped porous carbon composite material.
  • step 4 forming a noble metal in the pores of the nitrogen-doped porous carbon composite material is as follows:
  • the calcination temperature is 200 degrees Celsius to 500 degrees Celsius
  • the heating rate is 1 degree Celsius / minute to 20 degrees Celsius / minute
  • the time is 1 minute to 240 minutes
  • the temperature during the hydrogen reduction process is 150 degrees Celsius to 500 degrees Celsius
  • the heating rate is 1 degree Celsius / minute to 20 degrees Celsius / minute
  • the time is 1 minute to 360 minutes
  • the hydrogen flow rate is 20 ml / minute to 200 ml / minute.
  • the reducing agent is at least one of NaBH4, HCOOH, and hydrazine hydrate, and the molar ratio of the reducing agent to the precious metal precursor in the precious metal precursor solution is (1 to 1000): 1.
  • the metal source is cerium nitrate, zirconium nitrate, aluminum nitrate
  • the solvent is water
  • the nitrogen-containing biomass is bamboo, chitin, carboxymethyl chitin, chitosan, and carboxymethyl At least one of a base chitosan and glucosamine hydrochloride.
  • the mass ratio of the metal source to the nitrogen-containing biomass in step 2) is (0.05-2): 1.
  • the calcining time in the first calcining process is 0.1 hour to 5 hours.
  • the carbonate ion or bicarbonate ion in the porogen can react with the metal ion in the metal source to obtain a metal precipitate, and the metal precipitate is uniform. Distribution; on the other hand, the porogen and metal precipitate can be decomposed during the subsequent calcination process, and the generated gas can promote the formation of multiple pores in the nitrogen-doped porous carbon material. During the calcination process, metal precipitates decompose to form nano-scale metal oxides. The metal oxide is finally uniformly distributed in the nitrogen-doped porous carbon material, and a part of the surface is exposed through the pores.
  • the porogen does not need to be excessive relative to the metal source, and the carbonate or oxalate in the porogen Even if it is transferred to the metal precipitate, the metal precipitate will also decompose, and the generated gas will also form a porosity effect.
  • the present invention also provides an application of a composite catalyst in a catalytic hydrogenation reaction.
  • the composite catalyst is used as a catalyst in a selective hydrogenation reaction of an unsaturated ketone or a biotin precursor.
  • the structure of the biotin precursor is as follows: :
  • the unsaturated ketone is 6-methyl-5-hepten-2-one, 6,10-dimethyl-5-undecen-2-one, 6,10-dimethyl-5 , 9-undecanedien-2-one, 6,10,14-trimethyl-5-pentadecen-2-one, 6,10,14-trimethyl-5,9-pentadecane At least one of diene-2-one and 6,10,14-trimethyl-5,9,13-pentadecantrien-2-one.
  • the composite catalyst can be reused multiple times.
  • FIG. 1 is a scanning electron microscope photograph of the nitrogen-doped porous carbon composite material described in Example 1.
  • FIG. 1 is a scanning electron microscope photograph of the nitrogen-doped porous carbon composite material described in Example 1.
  • FIG. 2 is a transmission electron microscope photograph of the nitrogen-doped porous carbon composite material described in Example 1.
  • FIG. 2 is a transmission electron microscope photograph of the nitrogen-doped porous carbon composite material described in Example 1.
  • FIG. 3 is a transmission electron microscope photograph of the composite catalyst described in Example 1.
  • FIG. 3 is a transmission electron microscope photograph of the composite catalyst described in Example 1.
  • FIG. 4 is an X-ray diffraction pattern of the nitrogen-doped porous carbon composite material and the composite catalyst described in Example 1.
  • FIG. 4 is an X-ray diffraction pattern of the nitrogen-doped porous carbon composite material and the composite catalyst described in Example 1.
  • FIG. 5 is a schematic structural diagram of a selective hydrogenation reaction using a composite catalyst according to the present invention.
  • the invention provides a method for preparing a composite catalyst.
  • the preparation method includes the following steps:
  • Nitrogen-containing biomass and a porogen are sequentially added to the premix, and a metal source is reacted with the porogen to obtain a mixture containing a metal precipitate, wherein the porogen is ammonium bicarbonate, At least one of ammonium carbonate, ammonium oxalate, ammonium oxalate, and oxalic acid, and the molar ratio of the metal source to the porogen is 1: (1-20);
  • the mixture is first calcined under an inert atmosphere at 500 degrees Celsius to 1200 degrees Celsius to obtain a nitrogen-doped porous carbon composite material having multiple channels, wherein the nitrogen-doped porous carbon composite material includes a nitrogen-doped porous material.
  • a carbon material and a metal oxide which are uniformly distributed in the nitrogen-doped porous carbon material and a part of the metal oxide is exposed through the channel;
  • a noble metal is formed in the pores of the nitrogen-doped porous carbon composite material, so that the noble metal is tightly bound to oxygen atoms in the exposed metal oxide.
  • the metal source generally selects a metal oxide that can support a noble metal catalyst.
  • the metal source is required to be soluble in the solvent.
  • the metal source may be cerium nitrate, zirconium nitrate, or aluminum nitrate, and the solvent may be water.
  • the ratio of the metal source to the solvent is not limited.
  • the ratio of the mass of the metal source to the volume of the solvent is (1 g to 10 g): 100 mL.
  • the nitrogen-containing biomass is at least one of bamboo, chitin, carboxymethyl chitin, chitosan, carboxymethyl chitosan, and glucosamine hydrochloride.
  • the nitrogen-containing biomass contains a nitrogen element and a carbon element, and serves as a nitrogen source and a carbon source.
  • the nitrogen-containing biomass is insoluble in the solvent.
  • the metal source reacts with a portion of the porogen to form a precipitate.
  • the precipitate is formed by carbonate ions and metal ions.
  • Another part of the excess porogen is decomposed in the subsequent calcination process to generate a gas, which can play a role of pore formation, and a plurality of pore channels are formed in the nitrogen-doped porous carbon material.
  • the mass ratio of the metal source to the nitrogen-containing biomass may be (0.05-2): 1, and preferably, the mass ratio of the metal source to the nitrogen-containing biomass is (0.5-2): 1.
  • stirring was continued for 0.1 to 10 hours.
  • the obtained mixture is actually a suspension, in which the resulting precipitate and nitrogen-containing biomass are insoluble in the solvent, but are uniformly distributed in the mixture, and the mixture is a suspension.
  • step S2 and before step S3 the mixture is dried, and the specific drying process may be: drying at a temperature of 60 degrees Celsius to 180 degrees Celsius.
  • the first calcination time may be 0.1 to 5 hours.
  • the specific first calcination process is as follows: the temperature is raised to 500 ° C. to 1200 ° C. at 2 ° C./min to 30 ° C./min, and calcined at 500 ° C. to 1200 ° C. for 0.1 h to 5 h; finally, the temperature is naturally reduced to room temperature.
  • the first calcination temperature is 600 ° C to 900 ° C.
  • the noble metal is at least one of Pd, Pt, Ru, Rh, Ir, and Au.
  • the supported amount (ie, the mass fraction) of the noble metal in the composite catalyst can be controlled without limitation.
  • the process of the impregnation method is as follows: the nitrogen-doped porous carbon composite material is immersed in a precious metal precursor solution; the soaked nitrogen-doped porous carbon composite material is sequentially subjected to a second calcination and hydrogen reduction, and the Noble metals are formed in the pores of the nitrogen-doped porous carbon composite.
  • the calcining temperature in the second calcining process is 200 degrees Celsius to 500 degrees Celsius, the heating rate is 1 degree Celsius / minute to 20 degrees Celsius / minute, and the time is 1 minute to 240 minutes; the temperature in the hydrogen reduction process is 150 degrees Celsius to 500 degrees Celsius, heating rate is 1 degree Celsius / minute to 20 degrees Celsius / minute, time is 1 minute to 360 minutes, and hydrogen flow rate is 20 ml / minute to 200 ml / minute.
  • the calcination temperature is 300 degrees Celsius to 500 degrees Celsius, the heating rate is 5 degrees Celsius / minute to 10 degrees Celsius / minute, and the time is 60 minutes to 120 minutes; during the hydrogen reduction process, the temperature is 200 degrees Celsius to 400 degrees Celsius, and the temperature is increased.
  • the rate is 5 degrees Celsius / minute to 10 degrees Celsius / minute, the time is 60 minutes to 180 minutes, and the hydrogen flow rate is 40 ml / minute to 100 ml / minute.
  • the process of the liquid-phase reduction method is as follows: immersing the nitrogen-doped porous carbon composite material in a precious metal precursor solution; continuing to add a reducing agent to cause the precious metal precursor to react with the reducing agent, and doping the nitrogen Precious metals are formed in the pores of the porous carbon composite.
  • the noble metal precursor in the noble metal precursor solution referred to in the above-mentioned impregnation method and liquid phase reduction method may be PdCl 2 , H 2 PdCl 4 , Pd (NO 3 ) 2 , Pd (NH 3 ) 4 (NO 3 ) 2 , H 2 PtCl 6 ⁇ 6H 2 O, [Pt (NH 3 ) 4 ] (NO 3 ) 2 , Na 2 PtCl 4 ⁇ xH 2 O, H 8 C 14 N 2 Pt, PtCl 4 , Pt (C 5 H 7 O 2 ) 2 , C 10 H 14 O 4 Pt, (NH 4 ) 2 RuCl 6 , RuCl 3 , C 15 H 21 O 6 Ru, H 12 Cl 6 N 3 Rh, RhN 3 O 9 , RhCl 3 ⁇ 3H 2 O , IrCl 3 , Na 2 IrCl 6 ⁇ 6H 2 O, H 2 IrCl 6 ⁇ xH 2 O, [CH
  • the reducing agent in the liquid phase reduction is at least one of NaBH4, HCOOH, and hydrazine hydrate.
  • the molar ratio of the reducing agent to the precious metal precursor solution in the precious metal precursor solution is (1 to 1000): 1.
  • the invention also provides a composite catalyst.
  • the composite catalyst includes a support and a precious metal supported on the support.
  • the support is a nitrogen-doped porous carbon composite material having a plurality of pores.
  • the nitrogen-doped porous carbon composite material includes a nitrogen-doped porous carbon material and a metal. Oxide, the metal oxide is uniformly distributed in the nitrogen-doped porous carbon material, a part of the surface of the metal oxide is exposed through the channel, and the precious metal is tightly combined with the exposed metal oxide to achieve recombination,
  • the noble metal is at least one of Pd, Pt, Ru, Rh, Ir, and Au.
  • the dispersion degree of the noble metal in the nitrogen-doped porous carbon composite material is 75% to 95%.
  • the mass fraction of the precious metal in the composite catalyst is 0.1% to 10%; the mass fraction of the metal oxide in the composite catalyst is 2% to 30%; the nitrogen-doped porous carbon material A mass fraction occupied by the composite catalyst is 60% to 97.9%, and a mass fraction of the nitrogen element in the nitrogen-doped porous carbon material is 0.5% to 15%.
  • the present invention also provides an application of a composite catalyst in a catalytic hydrogenation reaction.
  • the composite catalyst is used as a catalyst in the selective hydrogenation reaction of unsaturated ketone or biotin precursor (X).
  • the unsaturated ketone is 6-methyl-5-hepten-2-one (I), 6,10-dimethyl-5-undecen-2-one (III), 6,10-dimethyl -5,9-undecanedione-2-one (V), 6,10,14-trimethyl-5-pentadecen-2-one (VI), 6,10,14-trimethyl At least 5-5,9-pentadecanedien-2-one (VIII), 6,10,14-trimethyl-5,9,13-pentadecantrien-2-one (IX) One.
  • Atomic emission spectroscopy was used to test the actual loading of Pd in the composite catalyst, and the result was 0.59%. This is basically consistent with the theoretical load of Pd.
  • FIG. 1 A scanning electron microscope test was performed on the nitrogen-doped porous carbon composite material, and the results are shown in FIG. 1. It can be seen from FIG. 1 that a rich channel structure can be clearly observed.
  • FIG. 3 A transmission electron microscope test was performed on the composite catalyst, and the results are shown in FIG. 3. Comparing FIG. 2 and FIG. 3, it can be seen that the morphology of FIG. 3 is basically unchanged compared to FIG. 2, and it is difficult to see the Pd metal in FIG. 3 because the particle size of the Pd particles is very small, below 1 nm.
  • the CO titration method (Note: The CO titration method is a carbon monoxide adsorption test for the dispersion of precious metals) was used to test the Pd dispersion and specific surface area of the composite catalyst. The test results were: Pd dispersion was 83%; The specific surface area of the catalyst was 135.3 m 2 g -1 .
  • the composite catalyst can be obtained by calcining in air at 300 ° C for 1 hour, and finally reducing the hydrogen at 300 ° C for 1 hour (hydrogen flow rate is 50 mL / min, and the heating rate is 5 ° C / min).
  • the method for preparing the composite catalyst in Example 2 is basically the same as the method in Example 1, except that the nitrogen-containing biotin is chitosan.
  • the composite catalyst can be obtained by reducing the hydrogen at 300 ° C for 1 hour (the hydrogen flow rate is 50 mL / min and the heating rate is 5 ° C / min).
  • CO titration was used to test the dispersion and specific surface area of Pd of the composite catalyst.
  • the test results were: the dispersion of Pd was 79%; the specific surface area of the composite catalyst was 126.8 m 2 g -1 .
  • the composite catalyst can be obtained by reducing the hydrogen at 300 ° C for 1 hour (the hydrogen flow rate is 50 mL / min and the heating rate is 5 ° C / min).
  • CO titration was used to test the dispersion and specific surface area of Pd of the composite catalyst, and the test result was: the dispersion of Pd was 76%.
  • the specific surface area of the composite catalyst was 115.5 m 2 g -1 .
  • CO titration was used to test the dispersion and specific surface area of Pd of the composite catalyst.
  • the test results were: the dispersion of Pd was 89%; the specific surface area of the composite catalyst was 138.7 m 2 g -1 .
  • the composite catalyst can be obtained by reducing the hydrogen at 300 ° C for 1 hour (the hydrogen flow rate is 50 mL / min and the heating rate is 5 ° C / min).
  • CO titration was used to test the dispersion and specific surface area of Pt of the composite catalyst.
  • the test results were: the dispersion of Pt was 91%, and the specific surface area of the catalyst was as high as 133.5 m 2 g -1 .
  • the composite catalyst can be obtained by reducing the hydrogen at 300 ° C for 1 hour (the hydrogen flow rate is 50 mL / min and the heating rate is 5 ° C / min).
  • the method of CO titration was used to test the dispersion and specific surface area of Ru of the composite catalyst.
  • the test result was: the dispersion of Ru was 82%, and the specific surface area of the composite catalyst was 133.9 m 2 g -1 .
  • a CO titration method was used to test the dispersion and specific surface area of Rh of the composite catalyst.
  • the test result was: the dispersion of Rh was 83%; the specific surface area of the composite catalyst was as high as 139.2 m 2 g -1 .
  • a CO titration method was used to test the dispersion and specific surface area of Ir of the composite catalyst.
  • the test result was: the dispersion of Ir was 81%, and the specific surface area of the composite catalyst was 128.4 m 2 g -1 .
  • the composite catalyst can be obtained by reducing the hydrogen at 300 ° C for 1 hour (the hydrogen flow rate is 50 mL / min and the heating rate is 5 ° C / min).
  • CO titration was used to test the dispersity and specific surface area of Au of the composite catalyst.
  • the test result was: the dispersity of Au was 88%, and the specific surface area of the composite catalyst was as high as 137.3 m 2 g -1 .
  • the composite catalyst catalyzes the selective hydrogenation of 6-methyl-5-hepten-2-one (I) as follows:
  • the composite catalyst catalyzes the selective hydrogenation of 6,10-dimethyl-5-undecen-2-one (III) as follows:
  • a 50 mL autoclave was used; 50 mg of the composite catalyst of Example 1 was added; the substrate 6,10-dimethyl-5-undecen-2-one (III) 15 mmol; ethanol 5 mL; hydrogen 2 MPa; reaction temperature 30 ° C; The reaction time is 4h.
  • the 6,10-dimethyl-5-undecen-2-one (III) conversion was 100%, and the 6,10-dimethyl-undecane-2-one (IV) selectivity was 99%.
  • the composite catalyst catalyzes the selective hydrogenation of 6,10-dimethyl-5,9-undecanedione-2-one (V) as follows:
  • the composite catalyst catalyzes the selective hydrogenation of 6,10,14-trimethyl-5-pentadecen-2-one (VI) as follows:
  • the composite catalyst catalyzes the selective hydrogenation of 6,10,14-trimethyl-5,9-pentadecanedien-2-one (VIII) as follows:
  • the composite catalyst catalyzes the selective hydrogenation of 6,10,14-trimethyl-5,9,13-pentadecantrien-2-one (IX) as follows:
  • the composite catalyst catalyzes the selective hydrogenation of 6-methyl-5-hepten-2-one (I) as follows:
  • the composite catalyst catalyzes the selective hydrogenation of 6-methyl-5-hepten-2-one (I) as follows:
  • a 50 mL autoclave was used; 50 mg of the composite catalyst of Example 7 was added; the substrate 6-methyl-5-hepten-2-one (I) 2 mmol; ethanol 5 mL; hydrogen 2 MPa; reaction temperature 40 ° C; reaction time 5 h.
  • the conversion of 6-methyl-5-hepten-2-one (I) was 100%, and the selectivity of 6-methyl-2-heptenone (II) was 97%.
  • the composite catalyst catalyzes the selective hydrogenation of 6-methyl-5-hepten-2-one (I) as follows:
  • a 50 mL autoclave was used; 50 mg of the composite catalyst of Example 8 was added; substrate 6-methyl-5-hepten-2-one (I) 15 mmol; ethanol 5 mL; hydrogen 2 MPa; reaction temperature 30 ° C; reaction time 4 h. 6-methyl-5-hepten-2-one (I) conversion was 100%, and 6-methyl-2-heptanone (II) selectivity was 99%.
  • the composite catalyst catalyzes the selective hydrogenation of 6-methyl-5-hepten-2-one (I) as follows:
  • the composite catalyst catalyzes the selective hydrogenation of 6-methyl-5-hepten-2-one (I) as follows:
  • a 50 mL autoclave was used; 50 mg of the composite catalyst of Example 10 was added; the substrate 6-methyl-5-hepten-2-one (I) 2 mmol; ethanol 5 mL; hydrogen 2 MPa; reaction temperature 50 ° C; reaction time 6 h.
  • the conversion of 6-methyl-5-hepten-2-one (I) was 100%, and the selectivity of 6-methyl-2-heptenone (II) was 97%.
  • the composite catalyst catalyzes the selective hydrogenation of biotin precursor (X), as follows:
  • a 50 mL autoclave was used; 200 mg of the composite catalyst of Example 1 was added; 2 mmol of the substrate biotin precursor (X); 5 mL of ethanol; 2 MPa of hydrogen; a reaction temperature of 40 ° C; and a reaction time of 3 hours.
  • Biotin precursor (X) conversion was 100% and biotin (XI) selectivity was 99%.
  • the composite catalyst catalyzes the selective hydrogenation of biotin precursor (X), as follows:
  • a 50 mL autoclave was used; 200 mg of the composite catalyst of Example 6 was added; 2 mmol of the substrate biotin precursor (X); 5 mL of ethanol; 2 MPa of hydrogen; a reaction temperature of 50 ° C; and a reaction time of 3 hours.
  • Biotin precursor (X) conversion was 100% and biotin (XI) selectivity was 99%.
  • Example 1 A 50 mL autoclave was used; 50 mg of the composite catalyst of Example 1 was added; substrate 6-methyl-5-hepten-2-one (I) 15 mmol; ethanol 5 mL; hydrogen 2 MPa; reaction temperature 30 ° C; reaction time 4 h. After the reaction, the composite catalyst was taken out by centrifugation, washed with ethanol three times, and dried at 40 ° C under vacuum and continued to be used for the reaction.
  • the application results of the composite catalyst are shown in Table 1. The composite catalyst can be applied 60 times repeatedly, with little change in activity and selectivity, and excellent stability.
  • the specific performance of the composite catalyst for the selective hydrogenation of biotin precursor (X) is as follows:
  • a 50 mL autoclave was used; 200 mg of the composite catalyst of Example 1 was added; 2 mmol of the substrate biotin precursor (X); 5 mL of ethanol; 2 MPa of hydrogen; a reaction temperature of 40 ° C; and a reaction time of 3 hours.
  • the composite catalyst was taken out by centrifugation, washed three times with ethanol, and dried at 40 ° C under vacuum and continued to be used for the reaction.
  • the results of the application of the composite catalyst are shown in Table 2.
  • the composite catalyst can be applied 35 times repeatedly with almost no change in activity and selectivity, and has excellent stability.

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Abstract

L'invention concerne un catalyseur composite. Le catalyseur composite comprend un support et un métal noble chargé sur le support, le support étant un matériau composite de carbone poreux dopé à l'azote comprenant une pluralité de canaux de pores, le matériau composite de carbone poreux dopé à l'azote comprend un matériau carboné poreux dopé à l'azote et un oxyde métallique, l'oxyde métallique étant réparti uniformément dans le matériau carboné poreux dopé à l'azote, une partie de la surface de l'oxyde métallique étant exposée à travers les canaux de pores, le métal noble étant étroitement lié à l'oxyde métallique exposé de façon à obtenir une composition, et le métal noble est au moins un élément parmi Pd, Pt, Ru, Rh, Ir et Au. L'invention concerne également un procédé permettant de préparer le catalyseur composite, et l'utilisation associée.
PCT/CN2019/071319 2018-08-31 2019-01-11 Catalyseur composite, procédé de préparation associé et utilisation associée Ceased WO2020042526A1 (fr)

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CN114540863A (zh) * 2022-01-14 2022-05-27 辽宁华融富瑞新能源科技股份有限公司 一种钌负载掺氮多孔碳析氢电催化剂的制备方法
CN115044927A (zh) * 2022-06-18 2022-09-13 福州大学 一种碳化物负载金属催化剂的制备方法及应用
CN116440897A (zh) * 2023-04-25 2023-07-18 湘潭大学 一种贵金属掺杂二氧化铈拟均相负载型催化剂及其制备方法与应用
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US10668460B2 (en) 2018-08-31 2020-06-02 Zhejiang Nhd Company Ltd. Composite catalyst, method for manufacturing composite catalyst and application thereof
CN110404573A (zh) * 2019-06-28 2019-11-05 中国科学技术大学 一种超小钯基合金材料的制备方法及应用
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CN114540863A (zh) * 2022-01-14 2022-05-27 辽宁华融富瑞新能源科技股份有限公司 一种钌负载掺氮多孔碳析氢电催化剂的制备方法
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CN116440897A (zh) * 2023-04-25 2023-07-18 湘潭大学 一种贵金属掺杂二氧化铈拟均相负载型催化剂及其制备方法与应用
CN116641093A (zh) * 2023-05-15 2023-08-25 常州大学 RuSe2/CeO2空心碳球异质结构电催化剂的制备方法及应用

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